JP2002544345A - Organic semiconductors based on statistical copolymers - Google Patents

Abstract

This invention relates to statistical copolymers of general formula (I) and their use in organic semiconductor devices: wherein m and j are the average number of repeat units of A and B such that: m=0.1-0.9, j=1-m, Q=10-50000; A and B are independently selected from hole transporting groups and electron transporting groups and are statistically distributed along the polymer chain; X and Z are selected from H, CN, F, Cl, Br, CO2CH3.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel compounds and the use of such compounds as conductive and electroactive substances. In particular, the present invention relates to the use of statistical copolymer systems comprising random side chains, or more specifically, covalently linked polymer chains having electroactive organic substituents.

It has been recognized that various organic compounds can be made to conduct electricity. The conductive mechanism can be either ionic or electronic.
Ionic conduction is most important in the formulation of polymeric substances with ionic compounds that can be considered as solutes in the polymer. Ion movement under an applied electric field will cause current flow. Typical materials where ionic conduction is important include blending of a polymer such as poly (ethylene oxide) with a lithium salt.

[0003] Electronic conduction occurs in organic compounds without the addition of ionic salts. There are various types of organic compounds that exhibit this type of conduction, including conjugated polymers such as poly (acetylene), poly (phenylenevinylene), and poly (thiophene). This type of conduction is also found in low molecular weight molecular solids such as N, N'-diphenyl-N, N'-ditolylbenzidine and aluminum tris 8-hydroxyquinolinate. Polymers that do not possess a conjugated backbone structure can also exhibit electronic conductivity. Such polymers include poly (vinyl carbazole) as a known example.

[0004] The electronic conductivity of these organic compounds depends on the insertion of charge into a substance.
Such charges can be introduced in various known ways, such as by doping with an oxidizing or reducing agent, chemical doping with a charge transfer agent, or insertion of a positive or negative charge from a conductive electrode. Examples of such known charge introduction are:
Chemical doping of poly (acetylene) with iodine as an oxidant, doping of poly (vinyl carbazole) with trinitrofluorenone as a charge transfer agent, low work function electrodes such as magnesium metal electrode by applying negative potential to the electrode Charge injection into a vapor-deposited thin film of 3-biphenyl-5- (4-t-butylphenyl) oxadiazole. This charge injection involves electrochemical reduction of the conductive material,
Alternatively, it can also be considered as an electrochemical doping of this material. Other electron-conducting organic compounds can be subjected to charge injection by a positive charge, typically applied through an electrode made of a high work function metal such as gold. Such charge injection is usually described as the injection of positive charges indicative of holes, and this description is understood to be equivalent to the extraction of electrons from a conducting material. A further route to charge generation in organic solids is the ionization of solid molecules under the influence of an electric field or incident light or both. In this case, one electron is removed from one molecule of the substance and captured by another molecule, or another part of the molecule. In this way, a pair of separate positive and negative charges is created, and either or both of these movements can contribute to conduction in the material.

[0005] Conduction in an electronically conducting organic solid involves charge transfer from one molecule to another in a real substance. Such charge transfer is explained by a charge hopping or charge tunneling mechanism that would allow electrons to overcome energy barriers between various molecules or between molecular subunits. In systems such as conjugated polymers, such as poly (acetylene) and poly (phenylenevinylene) charges,
The transfer of charge discontinuities in the regular binding arrangement of the polymer allows charge to flow along the conjugated chain. In such cases, the charge will typically be transferred by a large number of individual molecules through most of the material, and hopping or tunneling remains an important mechanism.

[0006] The use of organic conductive materials as semiconductors in electronic device assembly has been explored by many researchers. Field effect transistors have been assembled from organic compounds such as poly (acetylene), pentacene and poly (phenylenevinylene). Light emitting diodes include N, N'-diphenyl-N, N'-ditolylbenzidine, aluminum tris 8-hydroxyquinolinate, 3-biphenyl-5- (4-
Shown using a wide range of organic and molecular solids such as t-butylphenyl) oxadiazole and poly (phenylenevinylene). Such light emitting diodes are preferably assembled using at least two organic semiconductors that transport charges by transporting holes and electrons, respectively. By trapping charge carriers in the device until carrier recombination and emission can occur, such multilayer diodes tend to achieve higher efficiencies than single-layer devices. Photovoltaic devices have been assembled using compounds such as copper phthalocyanine and perylene bisbenzimidazole. Photoconductive materials have been prepared and are recommended for use as photosensitive layers in electrophotographic, photocopying and printing applications. Such photoconductive compositions include compositions based on poly (vinyl carbazole) doped with trinitrofluorenone.

[0007] Conducting polymers can be used as elements in optical storage and switching devices by exploiting the photorefractive effect. The photorefractive layer, due to the light emission ability of the charge, diffusion,
Alternatively, it has both the ability to transport charge carriers under an applied electric field and the linear electro-optic coefficient. Such properties are obtained by adding the selected dopant to the conducting polymer. Is C ₆₀ fullerene Suitable dopants for inducing the light emission ability of the charge. A suitable dopant that provides a linear electro-optic coefficient is dimethylaminonitrostilbene.

[0008] A number of disadvantages have been identified with the organic conductive materials described in the prior art. Among these disadvantages, chemical stability is an important parameter. Poly (acetylene), when doped, has high conductivity, but converts to a non-conductive product when exposed to air and must be handled and used in an inert gaseous body. It is believed that poly (phenylenevinylene) undergoes oxidation of the conjugated double bond of the main chain to produce a non-luminescent oxidation product. Additional degradation mechanisms have been identified or proposed for poly (phenylene vinylene) when incorporated into the device, such as sensitivity to ambient UV radiation. Molecular solids such as N, N'-diphenyl-N, N'-ditolylbenzidine can undergo crystallization, change form, or dissolve in the actuator. These effects can reduce or reduce the efficiency of the device at an early stage.

[0009] A further important disadvantage common to many organic conductive materials is that they are difficult or costly to process. Poly (acetylene) and poly (
(Phenylene vinylene) are both insoluble and infusible materials that use the precursor polymer route to make them for use in the device. Typically, a soluble precursor polymer is first synthesized and deposited on a prepared substrate. Next, using a combination of heating and reduced pressure to chemically convert the precursor polymer to the desired product,
It removes volatile small molecules, usually one or more by-products. Processing large quantities of the desired polymer into an opaque film requires tight control of this process, and entails the use of expensive and time consuming vacuum processing steps. It is difficult to further process the final polymer and difficult to achieve steps such as patterning and lithography. Many attempts have been made to provide a processable organic conductor solution. It is understood that substitution of alkyl, alkoxy and other mobile organic radicals on the polymer improves their solubility and processability. However, such substitutions may also commonly reduce the charge mobility of the system and reduce the desirability of this product for device fabrication. The substitution can also change the orbital energy of the system and change the potential required for charge injection into the material.

[0010] The low molecular weight conductive organic material used in the device must be deposited in a thin, uniform film. Such films are typically deposited by vacuum deposition from an electrically heated boat onto a substrate. This process is relatively time consuming and requires the use of expensive advanced vacuum handling equipment. The use of such a device takes a relatively long time due to the need to depressurize and degas the material and the device at various stages of the process. Thus, this route does not provide a means for low cost assembly of organic semiconductor devices.

One method known to alleviate this material processing problem is:
It is to provide a single layer device. This can be done in many ways. It has been shown that by using certain types of polymeric active substances, no further use is necessary. It is known to use so-called polymer mixtures, ie mixtures of polymers in which various functions are provided by the various polymers, ie electron transport, hole transport and, in some cases, luminescent functions. While these mixtures tend to be inefficient for a number of reasons, one of the reasons is that they tend to phase separate. The efficiency of a semiconductor device can be measured or evaluated in a number of ways, but these methods include quantum efficiency, the number of photons from the system per electron hole in the system, and brightness per watt. Measurement of a certain output efficiency.

[0012] Other polymer systems have also been developed, for example, incorporating both electron and hole transport functions on a single polymer backbone, for example, describing ABC triblock copolymers for LEDs. Macromol. Chem
. Phys. 199, 869-880, 1998. It is also known to incorporate hole or electron transport groups and chromophores (ie, luminophores) onto the polymer backbone to produce statistical copolymers, such as Bis
Berg et al., Macromolecules, 1995, 28, 386-89 and Caciallli et al., Synthetic Metals 75, 1995.
, 161-68.

[0013] Despite many efforts made to date, there remains a need for materials suitable for use in semiconductor devices having at least one of the following properties:

That is, an advantageous combination of electron work functions, one of the factors that determine the desired charge transport properties, particularly the potential required for charge injection from a metal electrode or semiconductor electrode into a polymer, charge carrier mobility, emission wavelength And the ability to control the bandwidth, ease of synthesis from readily available low cost starting materials, solubility, film forming ability and high physicochemical stability of the deposited film of the polymer during storage and operation of the device, Higher efficiency.

It has been unexpectedly found that processable conducting organic polymers can be prepared by random copolymerization of various organic derivatives. Such statistical polymers yield glass-forming polymers that do not contain any additional functional groups that can compromise stability. Even more surprising is the high charge transfer in such polymers,
Organic semiconductor devices constructed from these polymers have been found to provide excellent performance. Experimental equipment does not show any signs of crystallization of this statistical copolymer. In addition, the polymers show surprisingly good solubility in ordinary solvents and can be processed into uniform films suitable for device assembly simply by spin coating from solution. Therefore, the polymers satisfy the requirements for assembling organic semiconductor devices in a wide range of fields by a cheap and rapid processing method.

According to the present invention there is provided a statistical copolymer of general formula I:

[0017]

Embedded image In the formula, m and j are m = 0.1 to 0.9, j = 1-m, Q = 10 to 50,000
A and B are the average number of repeating units of A and B such that A and B are independently selected from hole and electron transport groups and are statistically distributed along the polymer chain; X and Z Is independently selected from H, CN, F, Cl, Br, and CO ₂ CH ₃ .

The electron transporting and hole transporting groups are such that there is a direct bond between the aromatic portion of the electron transporting group and the polymer backbone and a direct bond between the hole transporting group and the polymer backbone. Preferably, it is directly bonded to the skeleton.

Preferably, the direct bond is formed from a monomer containing a vinyl group bonded directly to a charge-bearing group.

It is preferred that the hole transport group is given by the following general formula II:

[0021]

Embedded image Wherein Ar ₁ is attached to the polymer backbone and is derived from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4,4′-biphenylene, 1,4-naphthylene and 2,6-naphthylene B and C are independently selected from the group of the Ar ₂ structure, Ar ₂ is selected from phenyl, biphenyl, 1-naphthyl and 2-naphthyl, and Ar ₂ is OR, NRR ′ and N (Ar ₃ 1) independently selected from ₂
One or two groups, wherein R and R ′ represent a C ₁ -C ₆ alkyl group, and Ar ₃ represents phenyl, biphenyl, 1-naphthyl and 2
-Naphthyl, and Ar ₃ may be optionally substituted with one or two groups independently selected from OR, N (Ar ₃ ) ₂ , and NRR ′.

Preferred groups of formula II are N, N-diphenyl-4-aminophenyl, 2- (N, N-diphenyl-6-amino) naphthyl, N, N-bis (4-dimethylaminophenyl) -4 -Aminophenyl, N-phenyl N-4-methoxyphenyl 4-aminophenyl, N-4-methylphenyl N-4-dimethylaminophenyl 4-aminophenyl, N-phenyl N-4-diphenylaminophenyl 4-aminophenyl N, N-bis-4-diphenylaminophenyl 4-aminophenyl, N-phenyl, N (4,4'-N ', N'-diphenylamino-biphenylyl) 4-aminophenyl, N-3-methylphenyl N- (4,4'-N'-phenyl-N'-3-methylphenylaminobiphenylyl) 4-aminophenyl, N-1-naph Le, N- (4,4'-N'- phenyl-N'-1-naphthyl amino biphenylyl) 4-aminophenyl, and the like.

Preferably, the electron transport group is provided by the following general formula III: _{Z 1 -E 1 - [- Z} 2 -E 2 -] n -Z 3 Formula III wherein, _{Z 1} is attached to the polymer backbone, and E1 and E2,

[0024]

Embedded image Wherein A, B and D are independently selected from CH and N in each ring;
And Q are S, O, NR ", CHR", CR "R", CH =
CH, N = N, N = CH and N = CR ", wherein Z ₁ and Z ₂ are
Single bond or 1,2-phenylene, 1,3-phenylene, 1,4-phenylene,
An Ar ₄ group selected from 4,4′-biphenylene, 1,4-naphthylene and 2,6-naphthylene, wherein Z ₃ is optionally substituted at one or two positions with C ₁ -C ₆ alkyl. Phenyl group, naphthyl group or biphenyl group,
R ″ is selected from C _{1 to} C ₆ alkyl groups and aryl groups, and n = 0, 1, or 2.

The aryl group for R ″ is preferably a phenyl group.

Preferred structures for E1 and E2 of Formula III include oxazole, oxadiazole, benzoxazole, benzothiazole, quinoxaline, thiadiazole, 1,2,4-triazine, phenylquinoxaline.

Overall preferred structures for Formula III include: 4- (5-phenyl-1,3,4-oxadiazolyl) phenyl, 4- (5- (t-butylphenyl) -1,3,4-oxadiazolyl) Phenyl, 6- (2,3-diphenyl) quinoxalinyl, 6- (2,3-dinaphthyl) quinoxalinyl, 4- (5- (t-butylphenyl) -1,3,4-oxadiazolyl) biphenylyl, 5- (2 -Benzoxazolyl-1,4-phenyl-2-benzoxazolyl).

Preferably, m = 0.3 to 0.7.

Q = 30-1000 is preferred.

In Formula I, the hole-transporting group and / or the electron-transporting group may also act as a light emitter (also referred to as a light-emitting substance), and / or a separate light-emitting substance may utilize such a substance. May be present in the device.

Structural and other advantages include an advantageous combination of the electronic work function, which is one factor that determines the desired charge transport properties, particularly the potential required for charge injection from a metal or semiconductor electrode to the polymer. Expressed on the basis of carrier mobility, ease of synthesis from readily available low cost starting materials, solubility, film forming ability, and high physicochemical stability of the polymer-adhered membrane in storage and handling equipment.

Statistical copolymers having a hole transporter and an electron transporter directly attached to the polymer backbone are provided between the aromatic portion of the electron transporter and the polymer backbone, and between the aromatic portion of the electron transporter and the polymer. It is considered to be particularly advantageous because of the reduced so-called parasitic accumulation added to the charge carrier, such that there is a direct bond between the backbone.

The compounds of formula I can be prepared by various routes. Vinyl (triphenylamine)
Can be prepared by reacting iodobenzene with diphenylamine. Either or both of these starting materials may have the appropriate substitution incorporated into the product triphenylamine. The reaction is known in the art, for example, Grimle
(Org Magn Reson, 15, 296, (1981)) or G
According to the procedure described by Authier et al. (Synthesis, 4, 383 (1987)), it can be advantageously carried out in the presence of finely divided copper by raising the temperature in a solvent such as dibutyl ether, dichlorobenzene and the like. . Vinyl substitution on triphenylamine can be achieved either by using vinyl-substituted iodobenzene or vinyl-substituted biphenyl in the above reaction, or by substitution of open sites on triphenylamine, or other functional group transformations.

An advantageous method for the synthesis of vinyltriphenylamine monomers uses the coupling of 4-iodobromobenzene with an optionally substituted diphenylamine in the presence of finely divided copper. The resulting bromotriphenylamine is converted to a Grignard derivative by treatment with magnesium metal in tetrahydrofuran and reacts with vinyl bromide to give the desired product.

Other methods of synthesizing vinyl triphenylamines will be apparent to those skilled in the art and can be used advantageously according to the specific nature and pattern of substitution desired.

The polymerization of the various monomers to form the copolymer of structure 1 can be achieved by known means of ionic or free radical polymerization and can be performed by thermal or photochemical initiation.

A further aspect of the present invention is a compound of the general formula II wherein the hole transporting and electron transporting groups are statistically distributed along the polymer chain and the degree of polymerization of the statistical copolymer is between 10 and 50,000. And electron transporting groups of the general formula III.

According to a further aspect of the present invention, the organic semiconductor device comprises an organic layer comprising either a statistical copolymer given by general formula I or a preferred embodiment of general formula I, wherein Comprising a substrate having the organic layer sandwiched therebetween.

The organic layer may comprise other or a plurality of other organic semiconductor materials, including a hole transport material and / or an electron transport material.

[0040] The organic layer may further comprise a luminescent material, which may also be referred to as a luminescent material.

The luminous body is preferably provided by any of the following: Coumarin-type luminescent dyes having a photoexcitable luminescence quantum efficiency of 0.6 or more, LR Morgan and JH in US Patent No. 5,446,157
Boron difluoride / pyrromethene dyes of the general type described by Boyer, coronene, rubrene, diphenylanthracene, decacyclene, fluorene,
Emission derivatives such as perylene and perylene esters and imides of such compounds, fluorinated condensed aromatic hydrocarbons such as fluorene cyanide derivatives, metal luminescence such as europium chelates, samarium chelates, terbium chelates and ruthenium chelates Chelate.

Preferably, the organic semiconductor device is an organic light emitting diode device.

It is preferable that at least one of the electrodes transmits light having the emission wavelength of the organic layer.
Other electrodes may be metals such as Sm, Mg, Li, Ag, Ca, Al or metal alloys such as MgAg, LiAl or double metal layers such as Li and Al or indium tin oxide (ITO). One or both electrodes may consist of an organic conductive layer.

The present invention will be described with reference to the drawings for purposes of example only.

FIG. 1 is a diagram illustrating an organic light emitting diode (OLED) device incorporating the materials of the present invention.

FIG. 2 is a plan view of the matrix multiplex address device of FIG.

FIG. 3 shows 0.5% PM580, 99.5% RJP5 used in the OLED device.
Film thickness 7 illustrating current / voltage characteristics for statistical copolymers comprising P
It is a figure at the time of 4.2 nm.

FIG. 4 shows a 0.5% PM580, 99.5% PM assembled into a device according to the present invention.
FIG. 7 shows the brightness versus current density measured for a statistical copolymer comprising RJP5P at a film thickness of 74.2 nm.

FIG. 5 shows a 0.5% PM580, 99.5% PM assembled into a device according to the present invention.
FIG. 4 shows the intensity versus wavelength measured for a statistical copolymer comprising RJP5P at a film thickness of 74.2 nm.

FIG. 6 shows a 0.5% PM650, 99.5% PM assembled into a device according to the present invention.
FIG. 4 is a diagram showing the luminance versus current density measured for a statistical copolymer comprising RJP5P at a film thickness of 76 nm.

FIG. 7 shows a 0.5% PM650, 99.5% PM assembled into a device according to the present invention.
FIG. 4 shows the intensity versus wavelength measured for a statistical copolymer comprising RJP5P at a film thickness of 76 nm.

FIG. 8 shows 0.5% PM650, 99.5% RJP5 used in the OLED device.
Film thickness 7 illustrating current / voltage characteristics for statistical copolymers comprising P
It is a figure at the time of 6 nm.

FIG. 9 shows the luminance versus current density measured for a statistical copolymer comprising a film thickness of 122.8 nm of 0.5% PM580, 99.5% RJP4W, assembled into a device according to the invention. 0.5% PM580, 99.5% RJP4
It is the figure which compared with the film thickness of 111.6 nm of X.

FIG. 10 shows a film thickness of 122.8 nm of 0.5% PM580 and 99.5% RJP4W.
5 shows the current density versus voltage measured for a statistical copolymer comprising 0.5% PM580 in dichlorobenzene assembled in an apparatus according to the present invention.
, 99.5% RJP4X compared to a total 5% solution, and film thickness 111
. 63.8 nm and film thickness 123.8n of 0.5% PM650, 99.5% RJP4W
FIG. 5 is a comparison of a 0.5% PM650, 99.5% RJP4X film thickness of 124.9 nm assembled into a device according to the present invention for a statistical copolymer comprising m.

FIG. 11 shows a film thickness of 123.8 nm of 0.5% PM650, 99.5% RJP4W.
Shows the luminance versus current density measured for a statistical copolymer comprising 0.5% PM650, 99.5% RJP assembled into a device in accordance with the present invention
It is the figure which compared with the film thickness 124.9nm of 4X.

FIG. 12 shows the emission spectrum for a sample comprising PM580 phosphor and copolymer RJP4W.

FIG. 13 shows an emission spectrum for a sample comprising PM650 illuminant and copolymer RJP4W.

FIG. 14 shows an emission spectrum from a sample comprising PM580 illuminant and blend RJP4X.

FIG. 15 shows an emission spectrum from a sample comprising a PM650 illuminant and a blend RJP4X.

Unless otherwise stated, all reagents used are Aldrich Chemical Company (A
ldrich Chemical Company).

The illuminants PM650 and PM580 were obtained from AG Electro-Optics, Inc., Tarpoarray Business Center, Farsidehouse, Tarpoarray, Cheshire.

The data shown in FIG. 3, FIG. 6, and FIG.
itley) using a 236 source measure unit.

The data shown in FIG. 4, FIG. 5, FIG. 7, FIG. 8, FIG. 9, FIG. 11, FIG. 12, FIG. 13, FIG. Obtained using

EXAMPLES The following compounds are illustrative examples synthesized according to the present invention.

Example 1 Synthesis of 4-acyl-triphenylamine 4-acyl-triphenylamine was prepared using a previously published procedure (CJ Fox).
And AL Johnson, J. et al. Org. Chem. , 1964, 29, 3
536) by the acylation of triphenylamine using acetyl chloride and anhydrous zinc chloride as catalyst.

Synthesis of 4-vinyl-triphenylamine 4-acyl-triphenylamine (31.6 g, 0.110 mol) and Al
(O ⁱ Pr) ₃ (44.5, 0.220 mol) was suspended in xylene (100 ml) and refluxed for 3 hours. During this time, nitrogen was passed through the reaction vessel and the top of the cooler to remove acetone produced during the reaction. The solution was cooled, and a white precipitate of an aluminum salt formed by pouring into water was removed by filtration. The layers were separated, the aqueous layer was washed with diethyl ether (2 × 150 ml), the combined organic extracts were dried over MgSO ₄ and the solvent was removed in vacuo to give a yellow solid. The solid was cooled to -78 ° C and recrystallized from hexane (100 ml) to give a white solid, collected by filtration and dried under reduced pressure (15.3 g, 0.056 mol, 51%). ¹ H NMR (200 MHz, CDCl ₃ ) d 7.4-6.8 (m, 20 H, aromatic C H ), 6.67 (dd, ³ J _HH 10
. 8 and _{17.58Hz, ArC H CH 2, 5.65} (d, 3 J HH 17.5
8Hz, ArCHC H _{2 ^{(trans)), 5.17 (d, 3}} J HH 10.9Hz
, ArCHC H ₂ (cis)). Elemental analysis: C 88.43%, H 6.39%, N 5.16% (C ₂₀ H ₁₇ N is
C 88.52%, H 6.32%, N 5.10%). Melting point: 87.5-89C.

Purification of Monomer 4-vinyl-triphenylamine was purified by silica column chromatography using hexane as eluent. The solvent was removed and redissolved in pentane which had been sufficiently degassed to dissolve the solid. The solution was stirred with activated carbon and filtered under nitrogen. It was then stirred with calcium hydride, filtered under nitrogen and finally stirred with silica and filtered under nitrogen. It was then cooled to −25 ° C. and the white solid formed was collected by filtration under nitrogen and dried under high vacuum for 7 days. From this point, the solid was handled in a nitrogen-filled dry box.

Example 2: Synthesis of oxadiazole monomers Synthesis of 2- (4-vinylphenyl) -5-phenyloxadiazole 2- (4-bromophenyl) -5-phenyl-oxadiazole ⁱ (2 0.0g
, 6.64 mmol) were dissolved in degassed toluene (30 ml). Pd (PPh ₃ ) ₄ (0.15 g, 0.133 mmol) and ⁿ Bu ₃ Sn (CHCH ₂ ) (
2.11 g, 6.64 mmol) was added under dry nitrogen. The solution was refluxed for 4 hours, cooled and evaporated to give a yellow solid. This solid was dissolved in toluene (20 ml), silica (20 g) was added, and the solvent was distilled off under reduced pressure. The solid except ⁿ Bu ₃ SnBr rinse with hexane placed on top of a short column of silica, then eluted the column with methanol. The methanol was evaporated and the residue was recrystallized from hexane to give 1.1 g of 2- (4-vinylphenyl) -5-phenyloxadiazole as white crystals, 67% (m.pt. ⁱⁱ 82-84 ° C). _{^{1 HNMR (CDCl 3, 300MHz)}} δ8.1~8.0 (m, 4H, aromatic C H), 7.6~7.6 (m, 5H, aromatic C H), 6.77 (dd, ³ J _HH 17.4 Hz and _{10.8Hz, C H CH 2),} 6.90 (d, 3 J HH 17
. _{^{4Hz, CHC H 2), (}} dd, 3 J HH 10.8Hz, CHC H 2).

Synthesis of 2- (3-vinylphenyl) -5-phenyloxadiazole 2- (4-bromophenyl) -5-phenyl-oxadiazole ⁱⁱⁱ (2.
(0 g, 6.64 mmol) was dissolved in degassed toluene (30 ml). Pd (PP
h _{3) 4} (0.15g, 0.133 mmol) and _{^{n Bu 3 Sn (CHCH 2)}} (2.11g, was added under dry nitrogen 6.64 mmol). The solution was refluxed for 4 hours, cooled and evaporated to give a yellow solid. This solid was dissolved in toluene (20 ml), silica (20 g) was added, and the solvent was distilled off under reduced pressure. The solid except ⁿ Bu ₃ SnBr rinse with hexane and put on top of a short column of silica, then eluted the column with methanol. The methanol was evaporated and the residue was recrystallized from hexane to give 0.90 g of 2- (3-vinylphenyl) -5-phenyloxadiazole as white crystals, 54% (m.pt. 75-76 ° C). Was. Observed value: C,
N,%; C ₁₆ H ₁₂ N ₂ O is C, 77.40; H, 4.87;
It requires 11.28%. ¹ H NMR (CDCl ₃ , 300 MHz) δ 8.1 to 8
. 2 (m, 3H, aromatic C H), 8.02 (dt, 1H, aromatic C H), 7.6
~7.4 (m, 5H, aromatic _{^{C H), 6.80 (dd,}} 3 J HH 17.7Hz and ^{_{10.8Hz, C H CH 2),}} 6.90 (d, 3 J HH 17.7Hz , CH
^{_{C H 2), 5.39 (dd}} , 3 J HH 0.8Hz, CHC H 2).

Example 3: Synthesis of 6-vinyl-2,3-diphenylquinoxaline Synthesis of 6-methyl-2,3-diphenylquinoxaline 1,2-diamino-4-methylbenzene (25.0 g, 0.20 mol ) And benzyl (43 g, 0.20 mol) were refluxed in ethanoic acid (250 ml) overnight.
The solvent was distilled off under reduced pressure, and the black residue was recrystallized three times from ethanol to give 6-
39.6 g of vinyl-2,3-diphenylquinoxaline, 65% (m.pt. 11
4.5-116 ° C (literature value ^iv 115-116 ° C). ¹ H NMR (CD
_{Cl 3, 300MHz) δ8.08 (d} , J8.4Hz, 1H, Hs of quinoxaline), 7.97 (bs, 1H, Hs of quinoxaline), 7.60 (dd, J8
. 4 Hz, J1.8 Hz, 1H, Hs of quinoxaline), 7.50 to 7.58 (
m, 4H, phenyl ring), 7.30 to 7.38 (m, 6H, phenyl ring), 2.
_{62 (s, 3H, CH 3} ).

Synthesis of 6-bromomethyl-2,3-diphenylquinoxaline 6-methyl-2,3-diphenylquinoxaline (5.0 g, 16.9 mmol) was dissolved in dry oxygen-free benzene (50 ml). This solution is refluxed,
A solid mixture of NBS (3.00 g, 16.9 mmol) and AIBN (0.1 g) was added over 30 minutes. The solution was then refluxed for 2 hours, cooled and water (3 ×
100 ml), dried over MgSO ₄ and evaporated to leave a light brown solid. This was recrystallized from hexane / toluene (1: 1, 80 ml) to yield 3.5 g, 56% of 6-bromomethyl-2,3-diphenylquinoxaline. ¹ HN
MR confirmed the presence of trace amounts of 6-methyl-2,3-diphenylquinoxaline. A small sample was recrystallized from acetone for characterization (m
. pt. 146-148 ° C). Found: C ,; H ,; N,%; C ₂₁ H ₁₅ N ₂ Br requires C, 67.21; H, 4.03; N, 7.47%. ¹ H NMR
(CDCl ₃ , 300 MHz) δ 8.16 (d, J8.7 Hz, 1H, Hs of quinoxaline), 8.16 (d, J2.2 Hz, 1H, Hs of quinoxaline), 7
. 78 (dd, J8.7 Hz, J2.2 Hz, 1H, Hs of quinoxaline), 7
. 48 to 7.56 (m, 4H, phenyl ring), 7.30 to 7.40 (m, 6H,
Phenyl _{ring), 4.71 (s, 2H,} CH 2 Br).

Synthesis of triphenyl (diphenylquinoxaline) phosphonium bromide 6-bromomethyl-2,3-diphenylquinoxaline (1.0 g, 2.7 mmol) and triphenylphosphine (0.70 g, 2.7 mmol) were converted to toluene ( 50 ml) and the solution was refluxed overnight. The precipitated white solid was collected by filtration and dried under reduced pressure to obtain triphenyl (diphenylquinoxaline) phosphonium bromide (1.58 g, 93%). ¹ H NMR (CDCl ₃ , 300 MHz
) Δ 7.1-7.8 (m, 29H, aromatic Hs), 5.82 (d, ² J _HP 13
_{Hz, 2H, CH 2 P)} . Obtained: C, H, N,%; C ₃₉ H ₃₀ N ₂ PB
r requires C, 73.47; H, 4.74; N, 4.39%. Melting point: Decomposed at around 200 ° C.

Synthesis of 6-vinyl-2,3-diphenylquinoxaline Triphenyl (diphenylquinoxaline) phosphonium bromide (44.0 g)
, 69 mmol) in dichloromethane (100 ml) and formaldehyde
(10 ml, 37% aqueous solution, 118 mmol) were added. Sodium hydroxide aqueous solution
The liquid (50 ml, 50% solution) was added dropwise over 30 minutes while stirring at high speed.
Stir for 30 minutes. The solution is diluted with dichloromethane, washed with water, MgSO ₄ And evaporated to dryness to give a pale yellow solid. Use hexane as eluent
Was purified by silica column chromatography to obtain 10.5 g of white crystals,
50% (m.pt. 122 to 123 ° C, literature value^v122-123 ° C). Real
Measurements: C ,; H ,; N,%; C₂₂H₁₆N₂Is C, 85.69; H, 5.2
3: N, 9.08% required.¹HNMR (CDCl₃, 300 MHz) δ8.
11 (d,³J_HH8.7 Hz, 1H, quinoxaline H), 8.10 (br, 1
H, quinoxaline H), 7.90 (dd,³J_HH8.7 Hz,⁴J_HH2.1
Hz, quinoxaline H), 7.45 to 7.55 (m, 4H, phenyl H), 7.
28-7.38 (m, 6H, phenyl H), 6.95 (dd,³J_HH(Cis)
11.1 Hz,³J_HH(Transformer) 17.7Hz, 1H, vinyl H), 6.0
0 (d,³J_HH(Transformer) 17.7 Hz, 1H, vinyl H), 5.47 (d
,³J_HH(Cis) 11.1 Hz, 1H, vinyl H).

[0074] The free-radical copolymerization of PDI is the polydispersity index ₌ M¯ w / M¯ _n.

(RJP5P): Copolymerization of 4-vinyl-triphenylamine and 6-vinyl-2,3-diphenylquinoxaline 1,2-diphenyl-6-vinylquinoxaline (0.60 g), 4-vinyltriphenyl Amine (0.60 g) and AIBN (19.71 mg, 120 μm
ol) was placed in an ampoule, and benzene (8 ml) was condensed into the ampoule under reduced pressure. Next, the solution in the ampoule was heated at 70 ° C. for 10 hours, cooled, and the product was poured into methanol (50 ml). The precipitated polymer was collected by filtration and dried under reduced pressure to obtain 0.82 g of a white powder.

(RJP4W): 4-vinyl-triphenylamine and 2-phenyl-5- (3
Copolymerization of '-vinylphenyl) -1,3,4-oxadiazole 2-phenyl-5- (3'-vinylphenyl) -1,3,4-oxadiazole (0.6 g), 4- Vinyl triphenylamine (0.60 g) and AIBN
(19.71 mg, 120 μmol) was placed in an ampoule, and benzene (5 m
l) was condensed into an ampoule. Next, the solution in the ampoule was heated at 70 ° C. for 10 hours, cooled, and the product was poured into methanol (50 ml). The precipitated polymer was collected by filtration and dried under reduced pressure to obtain 0.80 g of a white powder. GPC analysis _{(CHCl 3): M¯ n 15,700} , M¯ w 53,000, M¯ w / M¯ n 3.4.

For comparative purposes only, the following examples relate to the preparation of polymer mixtures: poly (2-phenyl-5- (3′-vinylphenyl) -1,3,4-oxadiazole) Preparation of Polymer Mixture of Poly (4-vinyltriphenylamine) and Poly (2-phenyl-5- (3′-vinylphenyl) -1,3,4-oxadiazole) (0.40 g, RJP4V) (4-Vinyltriphenylamine) (0.40 g, RJP4U) was dissolved in 10 ml of dichloromethane, stirred overnight, and filtered through a 0.2 μm filter into methanol (100 ml).
The precipitated polymer was collected by filtration and dried under reduced pressure to obtain 0.70 g of a white powder. ⁱ TF Osipova, GI Koldobskii, VA Ostrovskii, J. Org. Chem., USS
R (Engl. Transl.), 20, 1984, 2248. ii VI Grigor'eva, RS Mil'ner, Chem. Heterocycl. Compd. (Engl. Tra
nsl.), 4, 1968, 18. iii TF Osipova, GI Koldobskii, VA Ostrovskii, J. Org. Chem., U
SSR (Engl. Transl.), 20, 1984, 2248. iv Braun, Quarg, Angew. Makromol. Chem., 1975, 43, 125 v G. Manecke, U. Rotter, Makromol. Chem., 171, 1973, 49

The substances described according to the invention can be used in various devices. By way of example, one type of semiconductor device, an organic light emitting diode (OLED), suitable for incorporating the materials of the present invention is shown in FIG. The device comprises two electrodes 1a, 1b, at least one of which transmits light of the emission wavelength of the organic material 3 in one layer. Other electrodes include metals such as samarium (Sm), Mg, Li, Ca, Al, or metal alloys such as MgAg, LiAl, or dual metal layers such as Li and Al
Or it may be indium tin oxide (ITO). One of the electrodes 1a and 1b or both electrodes may be composed of an organic conductive layer. The work surface or substrate 2 may be made of any material that is sufficiently flat to allow for subsequent processing, for example, glass, silicon, plastic. The substrate 2 may transmit light emitted from the organic substance 3. Separately, one of the electrodes 1a, 1b may transmit. One layer of the organic substance 3 is sandwiched between the electrodes 1a and 1b. The organic material layer 3 has the following three characteristics: electron transport (ET); hole transport (HT); and light emission (LE).

In the present invention, the organic substance layer 3 comprises the substance given by the formula I,
Optionally, a separate light emitter may be present. In the absence of a separate light emitter, either the hole transporter group and / or the electron transporter group may further function as a light emitter.

It is preferable that the light emitting substance, that is, the light emitting body has high quantum efficiency.

The illuminant is preferably provided by any of the following: A coumarin-type luminescent dye having a photoexcitable luminescence quantum efficiency of 0.6 or greater, L in US Pat. No. 5,446,157. R Morgan and JH
Boroner difluoride / pyrromethene dyes of the general type described by Boyer, coronene, rubrene, diphenylanthracene, decacyclene, fluorene,
Luminescent condensed aromatic hydrocarbons such as perylene, perylene, luminescent derivatives of such compounds including esters and imides such as fluorene cyanide derivatives, metal luminescent chelates such as europium chelates, samarium chelates, terbium chelates, ruthenium chelates .

The organic material layer 3 may be attached to the electrode 1 a by any of the following techniques:
Thermal evaporation under reduced pressure, thermal spraying, chemical vapor deposition, spin deposition from solution or other conventional thin film methods.

The thickness of the organic material layer 3 is generally 30 to 2000 nm, preferably 50 to 500 nm.
nm. The device may include layers 4a and 4b located next to the electrodes 1a and 1b, which layers may be conductive or insulating, as a barrier to the diffusion of electrode material or The layer at the interface between 1a, 1b and the organic material layer 3 may act as a barrier to chemical reactions. 4a and 4
Examples of suitable materials for b include emeraldine, which prevents indium diffusion from the ITO electrode to the organic material layer 3, or for the same reason, phthalocyanine copper may be used, or the lithium electrode and the organic material may be used. The addition of a thin layer of lithium or magnesium fluoride (about 0.5 nm) at the interface with layer 3 may be used.

The device of FIG. 1 may be a single pixel device, or may be an addressed matrix. An example of an addressed OLED matrix is shown in the plan view of FIG. The display of FIG. 2 has the internal structure described in FIG. 1, but the substrate electrodes 5 are arranged in strip-like rows 5l to 5m, and also column electrodes 61 to 6n.
Which form an mxn matrix of addressable elements or pixels. Each pixel is formed by the intersection of a column electrode and a column electrode.

The column driving device 7 supplies a voltage to each column electrode 5. Similarly, the column driving device 8 supplies a voltage to each column electrode. Control of the applied voltage is provided by control logic 9 which receives power from voltage source 10 and timing from clock 11.

The following is a method of assembling a device incorporating the material prepared in Example 1 for illustration purposes only.

Example of equipment assembly 4.5% by weight of the polymer (99.5%) mixture produced by copolymerization of Examples 1 and 3 with dichlorobenzene in combination with the emitter PM580 (0.5%) Was dissolved. This solution was deposited on an indium tin oxide coated glass substrate, which was then centrifuged at 3000 rpm for 30 seconds. Remove this board from the spinner,
Placed on a hot plate at 75 ° C. for 10 minutes to blow off residual solvent. A uniform polymer film was deposited by this means. A cathode comprising a 100 nm layer of magnesium and a 100 nm layer of silver was deposited on the uniform polymer layer by thermal evaporation. The resulting film thickness was about 74.2 nm. The silver cathode layer may be deposited by thermal evaporation under a high vacuum using an evaporation mask. This mask was made of a series of 3.5 mm diameter annular holes, resulting in an array of annular electrode pads deposited on the organic layer. The sample was removed from the vacuum chamber and the electrical connection was contacted to the ITO using indium solder and to the silver pad using copper wire. Each device defined by the metallized area of one silver pad was found to function both as a rectifier and as a light emitting diode.

As further examples, a 5% solution in dichlorobenzene (0.5% PM580: 99.5% RJP4W), film thickness 124.9 nm, in dichlorobenzene (0.5% PM580: 99.5% RJP4X) 5% solution, film thickness 111.6 nm, 5% solution in dichlorobenzene (0.5% PM650: 99.5% RJP4W), film thickness 123.8 nm, film thickness in dichlorobenzene (0.5% PM650: 99.5%) RJP4X) 5% solution, film thickness 122.8 nm.

All samples were spin coated on ITO coated glass at 2000 rpm, all other processing conditions were as previously described.

RJP4X is a polymer mixture and is included for comparison purposes only.

In FIG. 11, the gradients are completely similar, but all devices made from the polymer mixture RJP4X were unsuccessful. Because the device could not transfer the same amount of current as the current made with the copolymer.

In FIG. 15, it is evident that there is a significant difference suggesting that phase separation has occurred in the polymer mixture, as compared to FIG. 13, and this data shows that the luminescent species of the mixture have different environments. Suggest that.

The compounds of the present invention can also be used in photosensitive devices such as photodiodes, photovoltaic cells,
It can also be used as a photosensitive layer and a photorefractive layer for electrophotography.

When the conductive polymers of the present invention can be used as elements of optical storage devices and switch devices by utilizing the photorefractive effect with reference to FIG. 1, the layer 3 has conductivity, luminescence and electro-optic properties. Comprising an organic material layer. Such properties can be obtained by the addition of suitable dopants to the conducting polymer as described by the present invention. Suitable dopants for inducing the light emission ability of charge include C ₆₀ fullerene. Suitable dopants that provide a linear electro-optic coefficient include:
Dimethylaminonitrostilbene is mentioned.

[Brief description of the drawings]

FIG. 1 illustrates an organic light emitting diode (OLED) device incorporating the materials of the present invention.

FIG. 2 is a plan view of the matrix multiplex address device of FIG. 1;

FIG. 3 illustrates a current / voltage characteristic for a statistical copolymer comprising 0.5% PM580, 99.5% RJP5P used in an OLED device, a film thickness of 74.2 n.
It is a figure at the time of m.

FIG. 4: 0.5% PM580, 99.5% RJP5 assembled into a device according to the invention.
FIG. 4 shows the luminance versus current density measured for a statistical copolymer comprising P at a film thickness of 74.2 nm.

FIG. 5: 0.5% PM580, 99.5% RJP5 assembled into a device according to the invention.
FIG. 4 shows the intensity versus wavelength measured for a statistical copolymer comprising P at a film thickness of 74.2 nm.

FIG. 6: 0.5% PM650, 99.5% RJP5 assembled into a device according to the invention.
FIG. 4 shows the brightness versus current density measured for a statistical copolymer comprising P at a film thickness of 76 nm.

FIG. 7: 0.5% PM650, 99.5% RJP5 assembled into a device according to the present invention.
FIG. 4 shows the intensity versus wavelength measured for a statistical copolymer comprising P at a film thickness of 76 nm.

FIG. 8 illustrates a current / voltage characteristic for a statistical copolymer comprising 0.5% PM650, 99.5% RJP5P used in an OLED device at a film thickness of 76 nm.

FIG. 9 shows the luminance versus current density measured for a statistical copolymer comprising 0.52.8% PM580, 99.5% RJP4W with a film thickness of 122.8 nm, and 0.5% of the 0.5% PM580 assembled into a device according to the present invention. It is the figure which compared with the film thickness of 111.6nm of 5% PM580 and 99.5% RJP4X.

FIG. 10 shows the current density versus voltage measured for a statistical copolymer comprising a film thickness of 122.8 nm of 0.5% PM580, 99.5% RJP4W, and dichlorobenzene assembled in a device according to the present invention. Medium 0.5% PM580, 99.5
The present invention relates to a statistical copolymer comprising 111.6 nm film thickness and 0.5% PM650, 99.5% RJP4W film thickness 123.8 nm compared to a total 5% solution of 5% RJP4X. 0.5% P assembled in the device according to
It is the figure which compared with film thickness 124.9nm of M650 and 99.5% RJP4X.

FIG. 11 shows the luminance versus current density measured for a statistical copolymer comprising a film thickness of 123.8 nm with 0.5% PM650, 99.5% RJP4W, and a brightness value of 0.5% assembled into a device according to the present invention. It is the figure which compared with the film thickness of 124.9nm of 5% PM650 and 99.5% RJP4X.

FIG. 12 shows emission spectra for a sample comprising PM580 phosphor and copolymer RJP4W.

FIG. 13 shows the emission spectrum for a sample comprising PM650 illuminant and copolymer RJP4W.

FIG. 14 shows an emission spectrum from a sample comprising a PM580 phosphor and a blend RJP4X.

FIG. 15 shows an emission spectrum from a sample comprising PM650 illuminant and blend RJP4X.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) H05B 33/22 H01L 29/28 (72) Inventor Utsud, Emma Louise Worcester-Doubleville, UK・ 14 ・ 3 ・ PS, Moulburn, St. Andrews Road, Dela Moulburn (72) Inventor Fueast, William J. Ames County Durham Day H. El-Ey, Durham City, Durham University South Road (72) Inventor Peace, Richard-Jillon County, Durham Day-Height, 1.3 El-Ey, Durham City, United Kingdom , Durham University South Road F-term (reference) 3K007 AB03 AB11 AB18 DB03 FA01 4J100 AB07P AB07Q AQ15Q AQ25Q BA31P BC43P BC43Q BC44Q BC45P BC49P BC51Q BC79Q CA04 JA46

Claims (15)

[Claims] 1. A compound of the general formula I [Wherein m and j are m = 0.1 to 0.9, j = 1-m, Q = 10 to 5000]
The average number of repeating units of A and B such that 0; A and B are independently selected from hole transporting and electron transporting groups and are statistically distributed along the polymer chain; X and Z is, H, CN, F, Cl , Br, independently selected from _CO 2 CH _3. ] Statistical copolymer. 2. An electron transporting group and a hole transporting group such that there is a direct bond between the aromatic portion of the electron transporting group and the polymer skeleton and a direct bond between the hole transporting group and the polymer skeleton. The statistical copolymer of claim 1, wherein is linked directly to the polymer backbone. 3. The method according to claim 1, wherein the hole transporting group has the following general formula II:[Wherein, Ar₁Is bonded to the polymer skeleton to form 1,2-phenylene, 1,3-phenylene.
Nylene, 1,4-phenylene, 4,4'-biphenylene, 1,4-naphthylene
And 2,6-naphthylene; B and C are Ar₂Independent of the group of structures
Chosen, Ar₂Is from phenyl, biphenyl, 1-naphthyl and 2-naphthyl
Chosen, Ar₂Are OR, NRR 'and N (Ar₃)₂Independently selected from
Optionally substituted with one or two groups, wherein R and R 'are C₁~ C ₆ Represents an alkyl group of Ar₃Is phenyl, biphenyl, 1-naphthyl and
Selected from 2-naphthyl, Ar₃Are OR, N (Ar₃)₂, Independent of NRR '
May be arbitrarily substituted with one or two groups selected. Given by
A statistical copolymer according to any one of claims 1 or 2. 4. A compound of the formula II wherein N, N-diphenyl-4-aminophenyl, 2- (N, N-diphenyl-6-amino) naphthyl, N, N-bis (4-dimethylaminophenyl) -4- Aminophenyl, N-phenyl N-4-methoxyphenyl 4-aminophenyl, N-phenyl N-4-dimethylaminophenyl 4-aminophenyl, N-4-methylphenyl N-4-dimethylaminophenyl 4-aminophenyl, N-phenyl N-4-diphenylaminophenyl 4-aminophenyl, N, N-bis-4-diphenylaminophenyl 4-aminophenyl, N-phenyl, N (4,4'-N ', N'-diphenylamino -Biphenylyl) 4-aminophenyl, N-3-methylphenyl N- (4,4'-N'-phenyl-N'-3-methylphenylamino 4. A compound according to claim 3, which is provided by one of the following: phenylyl) 4-aminophenyl, N-1-naphthyl, N- (4,4'-N'-phenyl-N'-1-naphthylaminobiphenylyl) 4-aminophenyl. Statistical copolymer as described. 5. The method according to claim 1, wherein the electron transporting group has the following general formula III: Z ₁ -E ₁ -[-Z ₂ -E _2- ] _n -Z ₃ Formula III wherein Z ₁ is bonded to the polymer skeleton; E2 is Wherein A, B and D are independently selected from CH and N in each ring;
And Q are S, O, NR ", CHR", CR "R", CH =
CH, N = N, N = CH and N = CR ", wherein Z ₁ and Z ₂ are a single bond or 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4 , 4'-biphenylene, a Ar ₄ groups selected from 1,4-naphthylene and 2,6-naphthylene, _{Z 3} is an optionally substituted alkyl of _C 1 -C ₆ in one or two positions It is a phenyl group, a naphthyl group or a biphenyl group, and R ″ is selected from C _{1 to} C ₆ alkyl groups and aryl groups, and n = 0, 1, or 2. The statistical copolymer according to claim 1 or 2 given by: 6. The statistical copolymer according to claim 5, wherein the aryl group is a phenyl group. 7. The statistics according to claim 5, wherein E1 and E2 of formula III are selected from oxazole, oxadiazole, benzoxazole, benzothiazole, quinoxaline, thiadiazole, 1,2,4-triazine, phenylquinoxaline. Copolymer. 8. A compound of the formula III wherein 4- (5-phenyl-1,3,4-oxadiazolyl) phenyl, 4- (5- (t-butylphenyl) -1,3,4-oxadiazolyl) phenyl, 6- (2,3-diphenyl) quinoxalinyl, 6- (2,3-dinaphthyl) quinoxalinyl, 4- (5- (t-butylphenyl) -1,3,4-oxadiazolyl) biphenylyl, 5- (2-benzoxazolyl The statistical copolymer according to claim 5, wherein the statistical copolymer is selected from the group consisting of 1,4-phenyl-2-benzoxazolyl). 9. A compound of the general formula I [Wherein m and j are m = 0.1 to 0.9, j = 1-m, Q = 10 to 5000]
X and Z are independently selected from H, CN, F, Cl, Br, CO ₂ CH ₃ ; and A and B are hole transports. Independently selected from a group and an electron transporting group, wherein the hole transporting group is statistically distributed along the polymer chain given by the following general formula II: Wherein Ar ₁ is attached to the polymer backbone and is derived from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4,4′-biphenylene, 1,4-naphthylene and 2,6-naphthylene B and C are independently selected from the group of the Ar ₂ structure, Ar ₂ is selected from phenyl, biphenyl, 1-naphthyl and 2-naphthyl, and Ar ₂ is OR, NRR ′ and N (Ar ₃ 1) independently selected from ₂
One or two groups, wherein R and R ′ represent a C ₁ -C ₆ alkyl group, and Ar ₃ represents phenyl, biphenyl, 1-naphthyl and 2
Selected from naphthyl, and Ar ₃ may be optionally substituted with one or two groups independently selected from OR, N (Ar ₃ ) ₂ , and NRR ′: Given by III: Z ₁ -E ₁ -[-Z ₂ -E _2- ] _n -Z ₃ Formula III wherein Z ₁ is attached to the polymer backbone and E 1 and E 2 are Wherein A, B and D are independently selected from CH and N in each ring;
Q represents S, O, NR ", CHR", CR "R", CH = CH,
N = N, N = CH and N = CR ″, wherein Z ₁ and Z ₂ are a single bond or 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4,4
'-Biphenylene, an Ar ₄ group selected from 1,4-naphthylene and 2,6-naphthylene, wherein Z ₃ is a phenyl group optionally substituted at one or two positions with C ₁ -C ₆ alkyl. , A naphthyl group or a biphenyl group, and R ″ is selected from C ₁ -C ₆ alkyl groups and aryl groups, and n = 0, 1, or 2.] Statistical copolymer. 10. A method in which a hole transporting group and an electron transporting group have statistical properties along a polymer chain.
So that the degree of polymerization of the statistical copolymer is 10 to 50,000.
General formula II[Wherein, Ar₁Is bonded to the polymer skeleton to form 1,2-phenylene, 1,3-phenylene.
Nylene, 1,4-phenylene, 4,4'-biphenylene, 1,4-naphthylene
And 2,6-naphthylene; B and C are Ar₂Independent of the group of structures
Chosen, Ar₂Is from phenyl, biphenyl, 1-naphthyl and 2-naphthyl
Selected, and Ar₂Are OR, NRR 'and N (Ar₃)₂Independently selected from
R and R 'may be optionally substituted with one or two groups₁ ~ C₆Represents an alkyl group of Ar₃Are phenyl, biphenyl, 1-naphthyl and
And 2-naphthyl, and Ar₃Are OR, N (Ar₃)₂, NRR
'May be optionally substituted with one or two groups independently selected from'. ] Positive
Hole transporting group, and general formula III Z₁-E₁-[-Z₂-E₂−]_n-Z₃ Formula III wherein Z₁Is attached to the polymer backbone, and E1 and E2 areWherein A, B and D are independently selected from CH and N in each ring;
And Q are S, O, NR ", CHR", CR "R", CH =
CH, N = N, N = CH and N = CR ", wherein Z₁And Z₂Is
Single bond or 1,2-phenylene, 1,3-phenylene, 1,4-phenylene,
Selected from 4,4'-biphenylene, 1,4-naphthylene and 2,6-naphthylene
Ar₄And Z₃Is optionally C in one or two positions₁~ C ₆ A phenyl group, a naphthyl group or a biphenyl group substituted with an alkyl of
R "is C₁~ C₆And n = 0, 1, or
Is 2. The electron transporting group of
Statistical copolymer that can be used. 11. The organic layer comprises a statistical copolymer provided by any one of claims 1 to 10 and comprises a substrate supporting said organic layer sandwiched between electrode structures. Organic semiconductor device. 12. The device according to claim 11, wherein the organic layer further comprises a light emitter. 13. A coumarin type luminescent dye having a quantum efficiency of photo-excitable luminescence of 0.6 or more, boron fluoride / pyrromethene dye, coronene, rubrene, diphenylanthracene, decacyclene, fluorene,
13. The device of claim 12, provided by one of a luminescent condensed aromatic hydrocarbon such as perylene, a metal luminescent chelate such as a europium chelate, a samarium chelate, a terbium chelate, a ruthenium chelate. 14. At least one of the electrodes transmits light of the emission wavelength of the organic layer, and the other electrode is formed of Sm, Mg, Li, Ag, Ca, Al or MgAg, LiA.
14. The device according to any one of claims 11, 12, 13 which is a metal alloy such as l or a metal comprising a double metal layer such as Li and Al or indium tin oxide (ITO). 15. An organic layer comprising a statistical copolymer according to any one of claims 1 to 10 and a substrate supporting said organic layer sandwiched between electrode structures. Light refraction device.